Monoazodyestuffs



drogen, alkyl,

Patented Apr. 11, 1933 UNITED, STATES LPATENT o rIcE' HUGO SCHWEITZER,

or LEVERKUSEN-WIESDORF, GERMANY, Assrenon 'ro GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A. CORPORATION OF DELAWARE MONOAZODYESTUFFS No Drawing. application filed January 2, 1931, Serial No. 506,309, and in Germany January 4, 1930.

" The presentinvention relatesto new monoazodyestufis, more particularly it relates to dyestu-fis of the probable general formula:

\N.OIS] 1 l wherein R stands for the residue of an aromatic diazo-compound of the benzene or naphthalene series, m and stand for by substituted alkyl, such as methyl, ethyl, hydroxyethyl, for hydrophenyl, phenyl or benzyl, y stands for hydrogen, an acyl, alkyl or phenyl group, such as an acetyl or benz'oyl. group, and n stands for one of the numbers one and two, and where in R and the naphthalene nucleus may be further, substituted by the sulfonic acid group, an arylsulfone group, the carboxylic acid group, the sulfoneamide group, halogen, the nitro group, the alkyl group, the alk oxy group, the hydroxy group,a substituted amino group, the components being selected in such a manner that at least one of them contains a sulfonic acid group. t My new dyestufis are prepared in the usual manner by coupling an aromatic diaz'o compound of the benzene or naphthalene series with an amino-hydroxy naphthalene containing one or two unsubstitutedor substituted sulfamino residues of a derivative or a substitution product thereof, the couplin being carried out either in an alkaline me um onthe hydroxy side or in an acid medium on the amino side. 40 The dyestuffs thus obtained are-generally red to dark powders, dyeing wool clearred to black shades fastto light,-often 'ofuriusual fastness to washing and fulling and of unobjectionable evenness. The new dyestuffs are likewise very suitable for. the

' described in' manufacture of pigments and for printing. Individual representatives of the new class of dyestuffs are also suitable" in dyeing cellulose acetate silk. 7. By employing diazo compounds, containing groups capable of forming metallic oomplexes, mordant dyeing azo dyestuffs are produced, which'likewise possess very notable fastness properties. i 7 The aminonaphtholsulfonic-acid-amides used as coupling components in my inven tion are prepared by treating the .ycorresponding acyl-aminonaphtholsulfochlorides British Specification 326226 with ammonia or a suitable base,'such.as ani line, dimethylamine, benzylamine, ethylbenzylamine and the like,'* and saponifying the acyl-amino group in the usual manner.

The invention is illustrated by the 1501- lowing examples, I without being limited thereto: 7

Example 1.17.3 parts .by weight of aniline-2 sulfonic-acid are diazotized in. the customary manner. The diazo-com'pound is run into an alkaline sodium carbonate solu-' tion of 53.9 parts by weight of l-acetylamino -'8-hydroXynaphthalene-3.G disulfodiKN- methylanilide.) When the coupling is com plete, the dyestuff of the following formula:

on NHoo oH. 3

is salted out, with suction and dried.

It dyes wool a clear red shade,which with stands even severe fulling, is very fast to 7 When the coupling is complete, the dyestufl having the following formula:

is salted out and Worked up by' the "known methods. It dyes wool a wine red shade, fast to fulling and of satisfactory evenness. Ewample "3.-18.9'parts by weightof 2- aminophenoll-sulfonic acid are diazotized in the customary manner. "The diazo compound is. run into an alkaline solution of 46.9 parts by weight of 1-a'mino-8-hydroxy naphthalene-3.6rdi (sulfanilide). When, the coupling is complete the dyestufi of the fol- I naphthol-s, such as for example, ,l-acetylamino-S-hydroxynaphthalenel.6 disulfo di (N-methylanilide) can likewise beused.

Example '4.21.8 parts by weight of 13 nitro-l-aniline-.6-sulfoniclacid are diazotized in the customary manner and coupled with 34.2 parts by weight of 2-amino-8-hydroxynaphthalene-6-sulfo-N-ethylanilide in alkaline sodium bicarbonate solution. The dyestuff of the following formula:

N=N- NH:

SOaH

S OzN V 'is worked up in the customary manner; it

dyes wool brick red shades, fast to fulling and'light'and of satisfactory evenness.

I Example 5.17.3 partsby weight ofaniline-2-sulfonic'acid are diazotized iIlthGiCllS' tomary manner. I The diazo compound is run into a cold solution, (diluted with a little water) of 37.9 parts by weight of the hydrochloride of 2-amino-8-hydroxynaphthalene- 6-sulfo-N-ethylanilide in 150 parts by weight of glacial acetic acid. Coupling begins at once. The excess of mineral acid is then neutralized by careful addition of neutral sodium acetate solution in such'a manner, that a faint reaction due to mineralacidpersists. When the coupling is complete the dyestuff of the following formula:

CiHs

v is salted out, converted into-itssodium salt and dried. It dyes wool a clear redv shade, fast to 'fulling and lightgand of verysatisfactory. evenness. i

..D.yest;ufi"s of similar properties are obtained by replacing the ani'line-Q-sulfonic acid'by other aromatic amino-sulfonicor ,carboxylicacids,:for example, by .chloro-aniline-sulfonic acids or by t-acetylamino-Laminobenzenesulfonic acids; furthermore the substitution for the 2-amino+8-hydroxynaphthalene-6-sulfo-N-ethylanilide droxynaphthalene-G-sulfonic acid amide, as 2 m'ethylamino-8-hydroxynaphthalene-6-sulfonic-l I-.me-th'ylanilide yields dyestuffs of the same fastness properties. r Example 6.25L3 p.artsby Weight of aniline-2.5-di-sulfonic acid arediazotized in the customary manner. "The diazo compound is addedto a solution, diluted with-water, of 37.9 parts by-weight of the hydrochloride or 2-amino-Shydroxymphthalene-fi sulfo. .N

of other 2-amino-8-hymethylanilide in 200 parts by weight of glacial acetic acid and the coupling and working up of the dyestuff carried. out as .described in Example 5. The dyestuff having the following formula:

S0311 l OH N=N I SOaH 2 H1N- /0 H3 SOzN dyes wool a red shade of satisfactory fastness to fulling and light, combined with satisfactory evenness.

When the aniline-2.5-disulfonic acid is replaced by aniline-QAL-disulfonic acid a red is likewise produced; replacement by 3-nitraniline-4.6-disulfonic acid yields a ruby shade of similar satisfactory properties. Example '7.--37.8 parts by weight of 2- amino 4: hydroXy-3'- carboxydiphenylsul fone-t-sulfonic acid are dissolved in 400' parts of water by means of a little alkali. After the addition of 6.9 parts by weight of sodium nitrite the solution is run at about 20 C. with thorough stirring into an 6X1 'cess of dilute hydrochloric acid. The diazo compound which separates, isffiltered with suction, made into a paste .witha little water and added to a solution, diluted with water, of 37 .9 parts by weight of the hydrochloride of 2-amino-8 -hydroxynaphthalene-6- sulfo-N-methylanilide in 100 parts by weight of glacial acetic acid. The working up of the dyestuff of the following formula:

which is quickly formed, is carried out in the customary manner. a

The dyestuff dyes wool a beautiful bluish red shade, which on after-chroming becomes somewhat bluer and very fast. When the 2 amino 4-hydroxy-3-carboxy-di-phenylsulfonel-sulfonic acid is replaced by 2- amino-2-hydroxy-3-carboxy 5 methyldiphenylsulfone-4-sulfonic acid and the 2-amino-8-hydroxynaphthalene G-SulfO-N-methylanilide-by the corresponding N-ethylorN hydroxy-ethyl compound or by Q-phenylamino-8-hydroxynaphthalene-6-sulfonic anilide similar dyestuffs are produced. When the 2 amino 4J- hydroxy-S carboxy diphenylsulfone--sulfonic acid is replaced by 4'-h droxy-3'-carboxy-2-amino-5 acetylamin iphenylsulfone and the 2-aminoe8-hydr0xynaphthalene-6-sulf0-N-methylanilide by the 2 amino-8-hydroxynaphthalene-6-sulfo- (4'3- hydroxy-3-carboxy anilide) a bordeaux shade results, which on after-chroming becomes somewhat yellower and very fast.

The sulfones used as diazo components in V this example are derived from the salicyclic sulfones described in British Specifications Nos. 2457 65 and 245865.

Example 8.22.3 parts by weight of 4- chloro-2-amino-plienol-6-sulfonic acid are diazotized in the known manner with 6.9 parts by weight of;. sodium nitrite in the presence of excess hydrochloric acid. The diazo solution is run into an alkaline sodium carbonate solution of 31.4 parts by weight of 2-aminoe.

5-hydroXynaphthalene-7-sulfanilide. When the coupling is complete, the dye-stufl' ofthe following formula:

I HO

instead of the 2-amino-5-hydroxynaphthalene-7-sulfanilide the corresponding amide, methylamide, cyclohexylamide, benzylamide, methylanilide or piperidide or other amines are used similar fast dyestuffs are produced, which are distinguished fromthe dyestuff of the example by possessing somewhat bluer or redder shades. On coupling molecular quantities of the diazo compound from 2-aminophenol'l-sulfamide and 2-famino-5- hydroxynaphthalene-7-sulfo-di-methylamide a monoazo dyestuif is obtained, the afterchromed dyeing of which onwool is likewise a very fast bluish black.

Example .9.2.- l parts by weight of 6- nitro-Q-aminophenols l-sulfonic acid are diazotized 1n the customary manner with 6.9

its

parts by weight of sodium nitrite in the presence of an excess of hydrochloric acidand ice. The diazo solution is then runinto a cold alkaline sodium carbonate solution of 31.4'parts by weight of 2-amino-8-hydroxynaphthalene-6-sulfanilide. When the coupling' is complete, the dystuff having the following formula:

HOaS' 'm QN=N i NH,

I OzN OH SOHNH is salted out, pressed and dried. wool anavy blue, which on after-chroming is converted into a bluish black, very fast to fulling and of excellent fastness to light.

By varying the diazo or coupling components as in'EXample 8, fast dyestuffs of similar shades are likewise obtained.

Example 10.24.8 parts by weight of 2- nitraniline--sulfonic acid are diazotized in the known manner with 6.9 parts'by weight of sodium nitrite and excesshydrochloric acid. The diazo compound is run slowly into an ice-cold solution of 82.8 parts by weight of Q-amino-8-hydroxynaphthalene-6-sulfo-N- methylanilide, towhich a little sodium bicarbonate has been added and when the coupling is complete the. dyestuff having the following formula:

I HO3S-N=N- NHz is worked up in the customary manner. It

cmco-mzrOrr:

It dyes conjunction with pigment are diazotized in the customary manner. The diazo compound is then run intoa'solu- 'tion of 35.7 parts by weight of 2-amino-8- hydroxynaphthalene -6- sulfo-N-hydroxyethylanilide in dilute hydrochloric. acid and the coupling and working up of the dyestufi' which corresponds to the following formula:

are carried outas indicated in Example 5.

The conversion of the dyestuff into a color lake or pigment is carried out by the known methods with or without the use of a substratum. I

l/Vhen employed as a coating as size color a clear bluish red, fast to water and of very satisfactory fastness to light is obtained. The barium lake of the dyestufi' is insoluble in the organic solvents customarily used in dyestuffs.

Example 12- -18? parts by weight of 2- amino-lunethylbenzenet-sulfonic acid are diazotized in the customary manner. The diazo compoundis run into an alkaline sodium carbonate solution of 53.9 parts by weight of 1-acetylamino-8-hydroxynaphthalene-3.6 disulfo-di- (N -methylanilide) When coupling is complete the dyestuff having the following formula:

NOzS

. Example 13:48.7 parts by weight of 1- amino-4-methylbenzene-2-sulfonic acid are diazotized in the usual manner. The diazo compound is introduced in an alkaline sodium solution of 40 parts byweight of Q-acetylamino-8-naphthol-6 sulfo- N (hydroxyethylno I -powders, dyeing wool anilide) When' the coupling *is' complete the dyestuff having the following formula .OH I Y I i Y T V I i l HOaS NH'OO-CHa no azo-H20 l eral formula wherein R stands for the residue of an aromatic diazo-compound of the benzene or naphthalene series, 00 and 00 stand for hydrogen, alkyl, hydrophenyl, phenyl or benzyl, y stands for hydrogen, an acyl, alkyl or phenyl group, n stands for one of the numbers one and two, the components of the dyestufi's being selected in such a manner that at least one of them contains a sulfonic acid group, and wherein the nuclei may be further substituted by substituents selected from the group consisting of the sulfonic acid group, an arylsulfone group, the carboxylic acid group, the sulfoneamide group, halogen, the nitro group, the alkyl group, the alkoxy group, the hydroxy group, a substituted amino group, being generally red to black clear red' to black shades fast to light.

2. Monoazo dyestuffs of the probable general formula:

, gen,

wherein R stands for the residue of an arc matic' diazo-compound :of the benzene or naphthalene series, w stands'for. alkyl, r13 stands for thebenzene nucleus, y stands for hydrogen, an acyl, alkyl or phenyl group, n stands for one of the numbers one'andtw'o, the components of thedyestufi's being selected in such a manner that-atleast one of them contains a 'sulfonic acid group and wherein thef'nuclei may be further substituted by substituents selected from the group consisting of the sul-fonic acid group,glan arylsulfone group, the carboxylic acid group'ythe sulfone'amide group, halogen, the nitro group, the alkyl group, the alkoxy group, the hydroxy group, a substitutedamino group, being generally red to black powders, dyeing wool clear red to black shades fast to light.

3. Monoazo dyestuffs of the probable general formula: g 7

wherein R stands for the residue of. an aromati'c diazocompound of the benzene or naphthalene series, as, stands for 'alkylfw stands for the benzene nucleus, 3/ stands for hydrogen, an' acyl, alkyl or phenyl' group, 1 stands for one of the numbers oneand two, the azo bridge standing in ortho-position to the group NH'y, the components of the dyestuffs being selected in such a manner that at least one of them contains a sulfonic acid group, and wherein the nuclei may be further substituted by substituents selected from the group consisting of the sulfonic acid group, an arylsulfone group, the carboxylic acid group, the sulfoneamidegroup, halogen, the nitro group, the "alkyl. group, the alkoxy group, the hydroxy group, a substituted amino group, being generally red to black powders, dyeing wool clear red to black shades fast to light.

4. Monoazo eral formula:

OHL

wherein R stands for theresidue of an'aromatic diazo compound of the benzene or naphthalene series, m stands for alkyl, m stands for the benzene nucleus, y stands for hydroan acyl, alkyl or jphenyl group, n stands for one of the numbers one and two, the azo bridge standingin ortho-position to the hydroxy I group of the naphthalene; nu-

dyestufis of the probable gencleus,the componentsrof the dyestuffs being a brownv powder,

dyeingwool from an acid selected insuch a manner that atleast one bath reddish-brown shades of good; fastness of them. contains a sulfonic' acid group,

xiv-herein the nuclei may be further substitutedby substituents selected from the group consisting of the sulfonicacid group,- an

'arylsulfone' group, the carboxylic acid group,

the sulf-oneamidegroup, halogen, the nitro group, the alkyl group, the alkoxy group, the

1D hydroxy group, a substituted amino group,

being'generally red to black powders, dyeing wool:clear red to black shades fast to light. I

5. Monoazo dyestufi's of the probable general formula:

' alkyl SOzN l: 05H; 11

wherein R stands fora benzene nucleus, alfuming and light-i kyl stands for an alkyl group from one to two carbon atoms, n standsfor one of the numbers one and two, and wherein the nuclei may be further substituted by substituents selected from the group-consisting of the sulphonic acid group, an arylsulfone group, the carboxylic acid group, the sulfonamide group, halogen,the nitro group the alkyl group, the alkoxy group, the hydroxy group, a substituted amino group, the components being selected in such amanner that at least one of them contains a sulfonic acid group, being generally red to black powders, dyeing Wool clear red to black shades-fastto light. '6. The dyestuff of the following ormula:

, 0Hv r 4o HzCC -N=N- .Nn-co-om.

sogN-om-om-on being in the form of its alkali metal salts a v red powder dyeing wool from an acidbath being in the form of itsalkali'metal salts and to fulling and light.

. The dyestuff of the following formula:

0on3 OH o,N I-N=N 1-NH: e

being in the form of its alkali metal salts-a bro wn-powder, dyeing wool from an acid n testimony whereof, I affix my signature.

HUGO SGHWEIT-ZER; 

